Plasticizers and plasticized compositions



u with irom 4 to 8 carbon atoms,

Patented Oct. 23, 1945 assassi- UNITED STATES PATENT OFFICE 2.3mmmsrrorzsas m msrrom voonlrosrrrozas William in BM in Powder Company.tion of mhmsslgnortoAtlns n,Dei.,aoorpora- No Drawing. Application March31, 1942,

a L Serial No. 437,030

llclalms.

The present invention relates to and plastlciaed compositions; Moreparticularly,

the invention concerns plasticizers for resinous,

Further objects are to provide a new and vain able class oi plasticizerstor, and plssticlzed compositions oi, the industrially importanthydrophobe polyvinyl resins, including polyvinyl chloride, polyvinylchloride acetate copolymer, polyvinyl acetate. and the polyvinylacetals.

A particular obieot oi the invention is the plastloising oi polyvinylbutyral resins by means oi my new plasticizers.

A further Object is to provide a new safety glassinterlayer ofplastlclled Polyvinyl bum-s1 The above and other objects will becomeapparent in the course orthe iollowins description and claims.

This application is a continuation in part of my application SerialNumber 323,583.

The vinyl type resinous polymers are an im portant class oi syntheticresins at the present time. In common with most other synthetic resins,however, most of the useful vinyl resins require the addition ofplasticizers to supply properties needed for practical uses. Theusetulness of a plasticizer depenih on many factors, notably,compatibility with the resin, stability, water resistance, lock 0!volatility, resistance to ultra violet light, properties imparted to theresin by the plastlcizer, and others. Successful plasticizers do nothave to rate well in every propplasticlzers 7 wherein,

city since certain applications of resinous plastics do not require alloithese properties. I

According to the presentinvention it has been discovered that the classor trlacetals and triketals oi hezltols. wherein the. acetal or hotelnouns are derived Irom aldehydes or ketones are highly eidcientplasticizers for resinous vinyl type Polymers. It

has further been discovered that the plasticlzed compositions resultingfrom the combination of a vinyl polymer and an acetal or ketal of theinvention are valuable plastics for use in the arts. Ibseonvenieno theacetals and hotels of the invention can be designated generically by theex- R=the hexavalent residue (CsHeOs') of a hexitol R1, Rs, and Rs=thedivalent hydrocarbon residues of non-aromatic aldehydos and ketoneshaving irom 4 to 8 carbon atoms.

Among the more important members oi this group may be mentioned thehexitol trl-n-butylliression idenes, notably mannitol tri-n-butylidene.from mannitoland n-butyraldehyde; the hexitol tri- 2-butylidenes, e. gl,sorbitol tri-fl-butylidene, from sorbitol and methyl ethyl ketone; andthe heititol tri-hexylidenes. such as, mannltol trl- (2- ethylbutylidene); from mannitol and B-ethyl butyraldehyde. The msnnitol andsorbi tol condensation products are prei'erred, but the other isomerichexitols can is starting materials.

Other carbonyl compounds which may be used as the source oi acetal orketal sroups include isobutyraldehyde, 2-methol pentanal-l, trimethylacetaldehyde, n-hex or capronaldehyde, the methyl pentanals, dimethylbutyraldchydes. trimethyl propionaldehyde, the propyl and isopropylmethyl ketones, and the four butyl methyl ketones, particularly themethyl i'so-butyl ketone, heptaldchydes, methyl amyl ketones,octaldehydes. methyl hexyl ketones, etc.

I may also employ cyclic starting materials such as cyclohexanone,methyl cyclopentanone, dimethyl or ethyl cyclobutanone, and cyclopentylaldehyde. Another group comprises unsaturated aldehydes and ketones,such as crotonaldehyde. hexadienal, vinyl crotonaldehyde and irresityloxide.

Particular interest, on the'score ofease'oi synthesis, and mild odor,attaches to the products from hexitols and the acyclic, saturatedaldehydes and methyl ketones, and within this group lie the preferredplasticizers of my invention.

As a class the compounds of my invention are colorless, virtuallyinsoluble in cold water. to sistant to hydrolysis by water and bases.compatible with vinyl type polymers, and with high boiling points, inthe range 160 to 190 at mm. pressure. They are either liquids or, incertain cases, and when hishly purified, low melt- 1118 solids.

The aldehydes and ketones may be combined with a given hexitol to givehomogeneous derivatives, or mixtures oi two or more aldehydes orketones, or aldehydes and ketones may be employed. I may likewise employmixtures oi! diflerent hexitols with one or more carbonyl compounds. Theuse of chemically mixed derivatives is advantageous from the thestandpoint oi compatibility and also freedom from crystallinity. Whereascrystallinity does not destroy the useiulness oi plasticizers tor vinylderivatives, it is frequently desirable to market, ship and useplasticizers which are liquid and free irom any tendency to crystallize.

In the case oi the higher aldehydes and ketones, and particularly withthe higher branched chain ketones, homogeneous tri-derivatives aredimcult to make because 01' lower reactivity and steric factors. Monooriii-derivatives are, however, relatively easy to make and it is thenadvantageous to react the remaining hexitol hydroxyl groups with alower, more reactive member oi the said aldehyde or ketone group, forinstance, n-butyraldehyde or methyl ethyl ketone.

ass'mss g. or a liquid boiling at 162-167 C. at 4 mm. pressure and 3'?g. of a liquid boiling at 172-177 C. at 4 mm. pressure. Analysis or bothfractions showed them to consist of isomeric terms of tributylidenesorbitol.

EKAMPLEZ Pursu'rron or Msm'ror. Tar-2-Emi. Burrtmm 637 g. 0! mannitolwere suspended in 2000 ml. of dioxane containing 1200 g. of 2-ethylbutyraldehyde, and 75 cc. of concentrated suliui-ic acid. The reactionmixture was kept at 70-80 C. for 00 minutes. with stirring. during whichtime the mannitol went into solution. The solution, after cooling, waspoured into cold water containing a slight excess of sodium hydroxideover that required for neutralizing the acid, the non-aqueous layercollected, washed with water, and then taken up in ether. Alter dryingover anhydrous calcium sulfate, the solvent was evaporated oil, and theproduct distilled at a pressure 0! 3 mm. Hg. It boiled at 185-187 C. atthis pressure.

The following table summarizes the properties or several acetals andketals prepared by similar methods:

Table I flolubli lgyin Pressure 9? Index of milling waterat RotationDsnsit Name Aldehyde or kstons pom hail-fit:- rcigsgt ion lMannitol-hutylidsns n-But dsh rec-1s: 3 ln vol.-- Lnsol.. 1. 458 +3.011.0640 Borbltol trl-butylldcns T 162-167 4 t o..-.. 0.03..-- 1.462 +9.071.0708 Monaitol tri-a-bntvlidene Methyl ethyl kstons.-.. lifrlifi 4.r.o..- 0.12..." 1.454 24.25 1.0707 iiii;iit n. us minutes-u" lit ilitei225 hi2 i'wi anal-0 y uy one 2-9 11 0 Sorbitel tri-fl-ethylbutylldsne o f..." 172-175 ll ...Co 1.60". 1.400 18.60 1.0443ManEltoltrl-mylidcne Methyl propy1ketone. 170-175 3 ".10..." um Borbltolttl-z-amylidene do 158-163 3 ...do..... 0.02-

' In absolute ethanol, 0-10.

EXAMPLE 1 Pmm'rroil or Soasiror. Tnrsu'rrtmlns 01 g. (0.5 mol) ofcrystalline sorbitol and 120 g. (1.66 mol) oi n-butyraldehyde were mixedwith 500 ml. of dioxane and to this were added 25 ml.

' oi concentrated H3304... This mixture was heated on a steam bath forone hour with stirring. At the end of this time the entire mass waspoured into 1500 ml. of water containing 40 g. of NaOH forneutralization. The aqueous solution was e tracted with 100 ml. of etherand the ether solution separated and dried with anhydrous calciumsulfate. After filtering of! the drier the volatile solvents weredistilled ircm the filtrate under reduced pressure and the residue wasdistilled under vacuum. The residue contained two fractions. 8

According to this invention I can plasticize a wide variety ofvinyl-type resins. These resins should be of the hydrophobe, that is,water-insoluble, type to ensure compatibility with my water-insoiubleplasticizers. Among this class 0! resins are polyvinyl chloride, variousvinyl chlorideacetate copolymers, the copolymers of vinyl chloride withother lower aliphat c vinyl esters, such as propionate, butyrate andchloracetate, copolymers of vinyl chloride with lower vinyl ethers, suchas ethyl, butyl, cyclohexyl, polymers of lower vinyl ketones such asmethyl vinyl, and certain polyvinyl acetsls. These polyvinyl acetals,ior which my plasticizers are particularly useful, should contain .nomore than free hydroxyl groups, and at least 60% or the acetal r upsmust have three to six carbon atoms. Examples of such polyvinyl acetalsinclude the safety glass type of butyral resin, containing about 20%free hydroxyl, 2% residual acetate, and 78% butyral. Othermodifications, in which up to but usually not more than 20%, of thehydroxyls in the resin are substituted by other aeetal groups, such asformal, acetal, or benzal, may be empl yed.

with polyvinyl chloride-acetate copolymer the triacetals and triketalsmay be used to formulate assassin shatter-resistant glass.

A solution of polyvinyl butyral, of the known as Vinylite XYSG, of theCarbide and Carbon Chemical Corporation. about 78 butyraldehydesubstitution, dual acetate'groups and 20% free alcohol groups, wasmadeup by dissolving the alcohol (formula #30), in the ratio oi! 15% byweight of resin to 85% alcohol. To this was i added manitoltri-n-butylidene, c1 60 parts of plasticizer to 100 parts the polyedpolyvinyl gsueh variety hi riorrnulawhich contained 2% resiresin indenatured in the proportion vinyl butyral. The mixture so produced was,

cast on glass a film. The film showed excellent adherence to the glass,moisture prootness, toughness, and resistance to ultraviolet light,combined with low volatility. The elongation o! the film. by standardtest, after-casting was 430%.

EXAMPLE4 A solution of polyvinyl chloride acetate was made by dissolving18.8 parts of the resin in a mixture containing 18.2 parts oi.cyclohexanone and 32.9 parts of toluene. all parts being by weight. Theresin used was the VYBH grade of Vinylite, made by Carbide and CarbonChemical Corp, and was a 90-10 copolymer of vinyl chloride and vinylacetate. Mannitol tri-2-butylidene, equal to 33% by weight of theresin,was added to the solution. The film obtained by casting this solution onglass or metal and air drying showed exceptional toughness andresistance to water. soap and alkali attack.

EXAMPLE 6 An alcoholic solution of polyvinyl butyral and mannitoltri-Z-butylidene was prepared, as described in Example 3, and cast on aglass plate. The coated glass plate was first air dried at roomtemperature, then baked at 120 C. for an hour. by which time it wasvirtually free of solvent. A top piece of plate glass'was placed uponthe plasticized butyral film. and the resulting glass sandwichintroduced into a vacuum oven where the pressure was reduced to -30 mm.of mercury. The temperature in the oven was raised to 300 C. for 3minutes. The vacuum was then released and the glass sandwich cooled. Theresulting composite showed excellent adhesion of the interlayer to theglass, even at F., and was perfectly clear.

Incorporation of the plastihized polyvinyl butyral into a glass sandwichmay also be carried out and the solvent evaporated to form Y which willoccur to by other means known to the such as by plaeing' preiorm sheetsor toils oi the interlayer between glass plates, and heating in a vacuumoven. the interiayer may beextruded hot onto glass, then covered andautoclaved, or the plastic composition may be reduced to a powder,distributed on the bottom plate. compacted with rollers, the cover glassput on, roller pressedand' finally sutoclaved in a vacuum oven. Again.the interlayer sheet can be inserted. in an underplasticiz'e'dcondition. between two sheets or glen whose inner surfaces are coatedwith over-plasticized resin. and the bond completed by heating with-orwithout pressure.

The foregoing examples are illustrative of the invention. However, itwill be understood that the invention is not limited to these specificapplications. but is capable of many variations those skilled in thisart. Also, numerous uses and applications 0! such plasticized productswill readily occur to those familiar with the art.

What is claimed is:

l. A composition comprising a hydrophobe resin selected irom the groupconsisting of polyvinyl esters and polyvinyl acetals, and a pissticizerconsisting essentially of a hexitol tricyclic acetal wherein the acetalgroups are selected from the group consisting oi! aliphatic aldehydeswith from 4 to 8 carbon atoms, cycloaliphatic aldehydes with from 4 to 8carbon atoms. aliphatic ketones with from 4 to 8 carbon atoms. andcycle-aliphatic ketones with from 4 to 8 carbon atoms.

2. A composition comprising a hydrophobe polyvinyl butyral resin, and aplasticizer consisting essentially of a hexitol tributylidene.

3. A composition comprising a hydrophobe polyvinyl butyral resin, and aplasticizer con-- sisting essentially of a hexitol tri-il-butyiidene.

4. A com osition as in claim 3 wherein the said hexitol is mannitol.

5. A composition comprising a hydrophobe polyvinyl hutyral resin, and aplasticizer consisting essentially of a hexitol tri-n-butylidene.

6. A safety-type glass interlayer comprising a polyvinyl butyral resinplasticiaed with a tributylidene of mannitol.

l. A safety-type glass interlayer comprising a polyvinyl butyral resinplasticized with the tributylidene of sorbitol.

8. A composition comprising a hydrophobe resin selected from the groupconsisting of polyvinyl esters and polyvinyl acetals.. and a plasticizerconsisting essentially of a hexitol tri-cyclic acetal 01' an aliphaticaldehyde with from 4 to 8 carbon atoms.

9. A composition comprising a hydrophobe resin selected from the groupconsisting 01' polyvinyl esters and polyvinyl acetals. and aplainticizer consisting essentially of a hexitol tri-cyclic acetal of analiphatic ketone with from 4 to I carbon atoms.

10. A composition comprising a hydrophobe resin selected from the groupconsisting 02 polyvinyl esters and polyvinyl acetals. and a plasticizerconsisting essentially of a hexitol trlbutyiidene.

11. A composition comprising a hydrophobe resin selected irom the groupconsisting of polyvinyl esters and polyvinyl acetals. and a pineticiserconsisting essentially of a hexitol tri-nbutylidene.

12. A composition comprising a hydrophobe resin selected from the groupoi poly- 4 mud:

vinyl esters and m m plu- 14. A mm comm-ma a 111mm than: mating,h'l-ireflnlelmltmmthunoupwnslsflmotpohbutylidln.

13. A composition {I Who Molar consisting essentially o! mannitol tan-3-otbolrl ethyl butylmene. letter! "1mm & WILHAMRHOIBI. 33. mm mm; at tiii-8- mm bumldem.

V mmmm or CORRECTION. v Patent No. 2,587,662. October 23, 1915- Quntrm1:. Bomb.

It is hereby eortuila flat error nppurs 1n the printed lpuiffaation orthe above nuzqbarad patent requiring oometiun 1: follow" 13312, in thetible, rn-t coluan minor, rm- "alumni-manna." rad --Hlnn1tp1tr1-buty1idenp--; m. a 1 1. 1m intent ahuuld be mad with 1m; correctiontharoig that filia -a0 n11 contorto 13:0 "and d the one in tlwa PatentOffice.

Signal and mlod this in flaw or January, A, n. 1%6.

1mm Frazer (Sal) First Assistant flaiuicnbr err-mm,

4 mud:

vinyl esters and m m plu- 14. A mm comm-ma a 111mm than: mating,h'l-ireflnlelmltmmthunoupwnslsflmotpohbutylidln.

13. A composition {I Who Molar consisting essentially o! mannitol tan-3-otbolrl ethyl butylmene. letter! "1mm & WILHAMRHOIBI. 33. mm mm; at tiii-8- mm bumldem.

V mmmm or CORRECTION. v Patent No. 2,587,662. October 23, 1915- Quntrm1:. Bomb.

It is hereby eortuila flat error nppurs 1n the printed lpuiffaation orthe above nuzqbarad patent requiring oometiun 1: follow" 13312, in thetible, rn-t coluan minor, rm- "alumni-manna." rad --Hlnn1tp1tr1-buty1idenp--; m. a 1 1. 1m intent ahuuld be mad with 1m; correctiontharoig that filia -a0 n11 contorto 13:0 "and d the one in tlwa PatentOffice.

Signal and mlod this in flaw or January, A, n. 1%6.

1mm Frazer (Sal) First Assistant flaiuicnbr err-mm,

